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EP2714770B1 - Procédé destiné à la fabrication de polyols de polyéther - Google Patents

Procédé destiné à la fabrication de polyols de polyéther Download PDF

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Publication number
EP2714770B1
EP2714770B1 EP12729042.7A EP12729042A EP2714770B1 EP 2714770 B1 EP2714770 B1 EP 2714770B1 EP 12729042 A EP12729042 A EP 12729042A EP 2714770 B1 EP2714770 B1 EP 2714770B1
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Prior art keywords
weight
parts
mixture
oxide
alkylene oxides
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German (de)
English (en)
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EP2714770A1 (fr
Inventor
Jörg Hofmann
Bert Klesczewski
Michael Schneider
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Covestro Deutschland AG
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Covestro Deutschland AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention relates to a process for the preparation of polyethercarbonate polyols from one or more H-functional starter substances, one or more alkylene oxides and carbon dioxide in the presence of at least one double metal cyanide catalyst, the polyethercarbonate polyols having at the chain end a mixing block of at least two alkylene oxides and flexible polyurethane foams obtainable therefrom ,
  • Activation in the context of the invention is a step in which a partial amount of alkylene oxide, optionally in the presence of CO 2 , is added to the DMC catalyst and then the addition of the alkylene oxide is interrupted, wherein due to a subsequent exothermic chemical reaction, a heat, the can lead to a temperature peak ("hotspot"), and due to the reaction of alkylene oxide and optionally CO 2, a pressure drop is observed in the reactor.
  • the activation step is the period of time from the addition of the subset of alkylene oxide compound, optionally in the presence of CO 2 , to the DMC catalyst until the evolution of heat occurs.
  • the activation step is preceded by a step for drying the DMC catalyst and optionally the initiator at elevated temperature and / or reduced pressure, wherein this step of drying is not part of the activation step in the context of the present invention.
  • WO-A 2008/058913 discloses a process for preparing polyethercarbonate polyols having at the chain end one block of pure alkylene oxide units, especially a block of pure propylene oxide units. WO-A 2008/058913 but does not disclose polyethercarbonate polyols having at the chain end a mixing block of at least two alkylene oxides.
  • the object of the present invention was to provide polyethercarbonate polyols which lead to flexible polyurethane foams which have increased compression hardness and increased tensile strength.
  • Such improved polyurethane flexible foam quality has in practice the technical advantage that they have an increased mechanical strength.
  • the preparation of the polyethercarbonate polyol according to step (i) is preferably carried out by addition of one or more alkylene oxides and carbon dioxide in the presence of at least one DMC catalyst to one or more H-functional starter substances ("copolymerization").
  • alkylene oxides (epoxides) having 2-24 carbon atoms can be used for the process according to the invention.
  • the alkylene oxides having 2-24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl- 1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-1,2-pentenoxide, butadiene monoxid
  • active groups having active H atoms are, for example, -OH, -NH 2 (primary amines), -NH- (secondary amines), -SH and -CO 2 H, preferably -OH and -NH 2 , more preferred is -OH.
  • H-functional starter substance for example, one or more compounds selected from the group consisting of mono- or polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thioalcohols, Hydroxy esters, polyether polyols, polyester polyols, polyester ether polyols, polyether carbonate polyols, polycarbonate polyols, polycarbonates, polyethyleneimines, polyetheramines (z. B. so-called Jeffamine ® from Huntsman, such as. For example, D-230, D-400, D-2000, T-403, T -3000, T5000 or corresponding BASF products, such.
  • polyetheramine D230, D400, D200, T403, T5000 polytetrahydrofurans
  • polytetrahydrofurans z. B. PolyTHF from BASF ®, such. as PolyTHF ® 250, 650S , 1000, 1000S, 1400, 1800, 2000
  • polytetrahydrofuranamines BASF product polytetrahydrofuranamine 1700
  • polyether thiols polyacrylate polyols, castor oil, the mono- or diglyceride of ricinoleic acid, monoglycerides of fatty acids, chemically modified mono-, di- and / or triglycerides of Fatty acids, and C 1 -C 24 alkyl fatty acid esters containing on average at least 2 OH groups per molecule, used ..
  • Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter compounds.
  • monofunctional alcohols can be used: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl 3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol., 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl, 3-hydroxybi
  • Suitable monofunctional amines are: butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
  • monofunctional thiols can be used: ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 3-methyl-1-butanethiol, 2-butene-1-thiol, thiophenol.
  • monofunctional carboxylic acids may be mentioned: formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.
  • suitable polyhydric alcohols are, for example, dihydric alcohols (such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1 , 5-pentanediol, methylpentanediols (such as 3-methyl-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis (hydroxymethyl) - cyclohexanes (such as, for example, 1,4-bis (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol,
  • the H-functional starter substances can also be selected from the substance class of the polyether polyols, in particular those having a molecular weight Mn in the range from 100 to 4000 g / mol. Preference is given to polyether polyols which are composed of repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, more preferably with a proportion of 50 to 100% propylene oxide units. These may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
  • Suitable polyether polyols made up of repeating propylene oxide and / or ethylene oxide units are, for example Desmophen ® -, Acclaim ® -, Arcol ® -, Baycoll ® -, Bayfill ® -, Bayflex ® - Baygal ® -, PET ® - and polyether polyols Bayer MaterialScience AG (such.
  • Desmophen ® 3600Z Desmophen ® 1900U
  • Acclaim ® polyol 2200 Acclaim ® polyol 4000i
  • Arcol ® polyol 1004 Arcol ® polyol 1010 Arcol ® polyol 1030 Arcol ® polyol 1070, Baycoll ® BD 1110 Bayfill VPPU ® 0789, Baygal ® K55, PET ® 1004 polyether ® S180).
  • suitable homo-polyethylene oxides are the BASF SE example Pluriol ® E-marks suitable homo-polypropylene oxides such as the BASF SE Pluriol ® P-marks suitable mixed copolymers of ethylene oxide and propylene oxide such as the Pluronic ® PE or PLURIOL ® RPE Brands of BASF SE.
  • the H-functional starter substances can also be selected from the substance class of the polyesterpolyols, in particular those having a molecular weight Mn in the range from 200 to 4500 g / mol.
  • Polyester polyols used are at least difunctional polyesters. Polyester polyols preferably consist of alternating acid and alcohol units.
  • acid components z As succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of said acids and / or anhydrides used.
  • Ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, diethylene glycol, Dipropylene glycol, trimethylolpropane, glycerin, Pentaerythritol or mixtures of the alcohols mentioned. If divalent or polyhydric polyether polyols are used as the alcohol component, polyester polyethers are obtained which can likewise serve as starter substances for the preparation of the polyether carbonate polyols. Preference is given to using polyether polyols having Mn 150 to 2000 g / mol for the preparation of the polyester ether polyols.
  • polycarbonate polyols such as polycarbonate diols
  • polycarbonate polyols can be used, in particular those having a molecular weight Mn in the range of 150 to 4500 g / mol, preferably 500 to 2500, for example by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and di- and / or polyfunctional alcohols or polyester polyols or polyether polyols.
  • polycarbonate polyols are found, for. B. in the EP-A 1359177 ,
  • the Desmophen ® C-types of Bayer MaterialScience AG can be used as polycarbonate such.
  • polyether carbonate polyols can be used as H-functional starter substances.
  • polyether carbonate polyols which are obtainable by the process according to the invention described here after step (i) or after step (ii) or after step (iii) are used.
  • These polyether carbonate polyols used as H-functional starter substances are prepared beforehand in a separate reaction step for this purpose.
  • the H-functional starter substances generally have a functionality (i.e., number of H atoms active per molecule of polymerization per molecule) of 1 to 8, preferably 2 or 3.
  • the H-functional starter substances are used either individually or as a mixture of at least two H-functional starter substances.
  • Preferred H-functional starter substances are alcohols of the general formula (II), HO- (CH 2 ) x -OH (II) where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • Examples of alcohols according to formula (II) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol.
  • H-functional starter substances are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of the alcohols of the formula (II) with ⁇ -caprolactone, for example reaction products of trimethylolpropane with ⁇ -caprolactone, reaction products of glycerol with ⁇ -caprolactone, and reaction products of pentaerythritol with ⁇ -caprolactone.
  • Preference is furthermore given to using water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyetherpolyols composed of repeating polyalkylene oxide units as H-functional starter substances.
  • the H-functional starter substances are one or more compounds selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, wherein the polyether polyol from a di- or tri-H-functional starter substance and propylene oxide or a di- or tri-H-functional starter substance, propylene oxide and ethylene oxide is constructed.
  • the polyether polyols preferably have a molecular weight Mn in the range of 62 to 4500 g / mol and a functionality of 2 to 3 and in particular a molecular weight Mn in the range of 62 to 3000 g / mol and a functionality of 2 to 3.
  • the polyether carbonate polyols are prepared by catalytic addition of carbon dioxide and alkylene oxides to H-functional starter substances.
  • H-functional means the number of H atoms active for the alkoxylation per molecule of the starter compound.
  • DMC catalysts for use in the homopolymerization of epoxides are in principle known in the art (see, eg US-A 3 404 109 . US-A 3,829,505 . US-A 3,941,849 and US Pat. No. 5,158,922 ). DMC catalysts, eg in US Pat. No. 5,470,813 . EP-A 700 949 . EP-A 743 093 . EP-A 761 708 . WO 97/40086 .
  • WO 98/16310 and WO 00/47649 have a very high activity in the homopolymerization of epoxides and allow the preparation of polyether polyols at very low catalyst concentrations (25 ppm or less), so that separation of the catalyst from the finished product is no longer required in general.
  • a typical example is the in EP-A 700 949 described highly active DMC catalysts containing a double metal cyanide compound (eg zinc hexacyanocobaltate (III)) and an organic complex ligand (eg tert-butanol) or a polyether having a number average molecular weight greater than 500 g / mol.
  • the double metal cyanide compounds contained in the DMC catalysts are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.
  • an aqueous solution of zinc chloride preferably in excess, based on the metal cyanide salt such as, for example, potassium hexacyanocobaltate
  • potassium hexacyanocobaltate is mixed and then dimethoxyethane (glyme) or tert- butanol (preferably in excess, based on zinc hexacyanocobaltate) is added to the resulting suspension.
  • dimethoxyethane (glyme) or tert- butanol preferably in excess, based on zinc hexacyanocobaltate
  • suitable metal salts are zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, ferrous sulfate, iron (II) bromide, ferrous chloride, ferric chloride, cobalt (II) chloride, cobalt ( II) thiocyanate, nickel (II) chloride and nickel (II) nitrate. It is also possible to use mixtures of different metal salts.
  • suitable metal cyanide salts are sodium hexacyanocobaltate (III), potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III) and lithium hexacyanocobaltate (III).
  • Suitable double metal cyanide compounds a) are zinc hexacyanocobaltate (III), zinc hexacyanoiridate (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobaltate (III).
  • suitable double metal cyanide compounds are, for example US 5,158,922 (Col. 8, lines 29-66). Zinc hexacyanocobaltate (III) is particularly preferably used.
  • organic complexing ligands added in the preparation of the DMC catalysts are, for example, in US 5,158,922 (see in particular column 6, lines 9 to 65), US 3 404 109 . US 3,829,505 . US 3,941,849 . EP-A 700 949 . EP-A 761 708 . JP 4 145 123 . US 5,470,813 . EP-A 743 093 and WO-A 97/40086 ) disclosed.
  • organic complex ligands water-soluble, organic compounds having heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the double metal cyanide compound used.
  • Preferred organic complex ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof.
  • Particularly preferred organic complexing ligands are aliphatic ethers (such as dimethoxyethane), water-soluble aliphatic alcohols (such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), compounds containing both aliphatic or cycloaliphatic ether groups as well as aliphatic hydroxyl groups (such as ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol mono methyl ether and 3-methyl-3-oxetan-methanol).
  • Highly preferred organic complexing ligands are selected from one or more Compounds of the group consisting of dimethoxyethane, tert-butanol 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetane methanol.
  • the metal salt eg zinc chloride
  • metal cyanide salt eg, potassium hexacyanocobaltate
  • organic complexing ligand eg, tertiary butanol
  • the organic complex ligand can be present in the aqueous solution of the metal salt and / or the metal cyanide salt, or it is added directly to the suspension obtained after precipitation of the double metal cyanide compound. It has proven to be advantageous to mix the aqueous solutions of the metal salt and the metal cyanide salt, and the organic complex ligand with vigorous stirring.
  • the suspension formed in the first step is subsequently treated with a further complex-forming component.
  • the complex-forming component is preferably used in a mixture with water and organic complex ligands.
  • a preferred method for carrying out the first step is carried out using a mixing nozzle, more preferably using a jet disperser as in WO-A 01/39883 described.
  • the isolation of the solid (i.e., the precursor of the inventive catalyst) from the suspension is accomplished by known techniques such as centrifugation or filtration.
  • the isolated solid is then washed in a third process step with an aqueous solution of the organic complex ligand (e.g., by resuspension and subsequent reisolation by filtration or centrifugation).
  • an aqueous solution of the organic complex ligand e.g., by resuspension and subsequent reisolation by filtration or centrifugation.
  • water-soluble by-products such as potassium chloride
  • the amount of the organic complex ligand in the aqueous washing solution is between 40 and 80 wt .-%, based on the total solution.
  • the aqueous washing solution further complex-forming component, preferably in the range between 0.5 and 5 wt .-%, based on the total solution added.
  • a first washing step (c-1) with an aqueous solution of the unsaturated alcohol is washed (eg by resuspension and subsequent reisolation by filtration or centrifugation), in order in this way, for example, water-soluble by-products, such as potassium chloride, from the catalyst of the invention remove.
  • the amount of the unsaturated alcohol in the aqueous washing solution is between 40 and 80% by weight, based on the total solution of the first washing step.
  • either the first washing step is repeated once or several times, preferably once to three times, or preferably, a non-aqueous solution, such as e.g. a mixture or solution of unsaturated alcohol and further complexing component (preferably in the range between 0.5 and 5 wt .-%, based on the total amount of the washing solution of step (c-2)), used as a washing solution and the solid so once or washed several times, preferably once to three times.
  • a non-aqueous solution such as e.g. a mixture or solution of unsaturated alcohol and further complexing component (preferably in the range between 0.5 and 5 wt .-%, based on the total amount of the washing solution of step (c-2)
  • the isolated and optionally washed solid is then, optionally after pulverization, at temperatures of generally from 20 to 100 ° C and at pressures of generally 0.1 mbar to atmospheric pressure (1013 mbar) dried.
  • a preferred method for isolating the DMC catalysts of the invention from the suspension by filtration, filter cake washing and drying is in WO-A 01/80994 described.
  • a mixture of ethylene oxide (EO) and propylene oxide (PO) is used as a mixture of at least two different alkylene oxides, wherein the molar ratio PO / EO of 15/85 used in step (ii) to 60/40, preferably from 15/85 to 40/60.
  • the polyether carbonate polyols resulting from step (ii) and containing a terminal mixing block of EO and PO preferably have a proportion of primary OH groups of from 10 to 90 mol%, particularly preferably from 20 to 50 mol%.
  • the average length of the mixed blocks of at least two different alkylene oxides prepared according to step (ii) is preferably 2.0 to 20.0 alkylene oxide units, more preferably 2.5 to 10.0 alkylene oxide units, each based on an OH group of polyether carbonate polyol.
  • the polyether carbonate polyols resulting after step (ii) and containing a mixing block of at least two alkylene oxides preferably have a hydroxyl number of 20 mg KOH / g to 80 mg KOH / g, more preferably from 25 mg KOH / g to 60 mg KOH / g ,
  • the average length of a pure alkylene oxide block prepared according to step (iii) is preferably from 2 to 30 alkylene oxide units, particularly preferably from 5 to 18 alkylene oxide units, each based on an OH group of the polyethercarbonate polyol.
  • the reaction according to step (iii) can be carried out, for example, in the presence of DMC catalysts, or in the presence of acidic catalysts (such as BF 3 ) or basic catalysts (such as, for example, KOH or CsOH).
  • the reaction according to step (iii) is carried out in the presence of a DMC catalyst.
  • the invention thus also Polyethercarbonatpolyole containing a terminal mixing block of at least two alkylene oxides, preferably a terminal mixing block of ethylene oxide (EO) and propylene oxide (PO).
  • EO ethylene oxide
  • PO propylene oxide
  • the molar ratio of PO / EO is from 15/85 to 60/40, preferably from 15/85 to 40/60.
  • the polyether carbonate polyols which contain a terminal mixing block of EO and PO have a proportion of primary OH groups of from 10 to 90 mol%, particularly preferably from 20 to 50 mol%.
  • Preferred subject matter of the invention are polyether carbonate polyols which have a terminal mixing block of at least two alkylene oxides, characterized in that the average length of the terminal mixing block of at least two different alkylene oxides of 2.0 to 20.0 alkylene oxide units, more preferably 2.5 to 10.0 alkylene oxide units (in each case based on an OH group of the polyethercarbonate polyol).
  • the polyether carbonate polyols according to the invention which contain a mixing block of at least two alkylene oxides preferably have a hydroxyl number of 20 mg KOH / g to 80 mg KOH / g, more preferably from 25 mg KOH / g to 60 mg KOH / g.
  • these polyether carbonate polyols according to the invention may contain at the chain end a pure alkylene oxide block which preferably consists of propylene oxide or ethylene oxide units, more preferably of propylene oxide units.
  • the average length of such a pure alkylene oxide block at the chain end is preferably 2 to 30 alkylene oxide units, more preferably 5 to 18 alkylene oxide units, each based on an OH group of the polyethercarbonate polyol.
  • the preferred subject matter of the invention is a process for producing flexible polyurethane foams having a bulk density in accordance with DIN EN ISO 3386-1-98 in the range from ⁇ 10 kg / m 3 to ⁇ 150 kg / m 3 , preferably from ⁇ 20 kg / m 3 to ⁇ 70 kg / m 3 and a compression hardness according to DIN EN ISO 3386-1-98 in the range of ⁇ 0.5 kPa to ⁇ 20 kPa (at 40% deformation and 4th cycle) by reaction of
  • Containing component A polyol formulation
  • the polyethercarbonate polyol according to component A1 is preferably obtainable by the above-described preparation process according to the invention.
  • Starting components according to component A2 are conventional polyether polyols.
  • Conventional polyether polyols in the context of the invention are compounds which contain alkylene oxide addition products of starter compounds having Zerewitinoff-active hydrogen atoms, ie polyether polyols having a hydroxyl number according to DIN 53240 of ⁇ 15 mg KOH / g to ⁇ 80 mg KOH / g, preferably ⁇ 20 mg KOH / g to ⁇ 60 mg KOH / g.
  • starter compounds having Zerewitinoff-active hydrogen atoms usually have functionalities of 2 to 6, preferably of 3, and preferably the starter compounds are hydroxy-functional.
  • hydroxy-functional starter compounds are propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,12-dodecanediol , Glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, methylol group-containing condensates of formaldehyde and phenol or mel
  • Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide and styrene oxide.
  • propylene oxide and ethylene oxide are fed to the reaction mixture individually, in a mixture or in succession. If the alkylene oxides are metered in succession, the products produced contain polyether chains with block structures. Products having ethylene oxide endblocks are characterized, for example, by increased levels of primary end groups, which impart advantageous isocyanate reactivity to the systems.
  • component A3 water and / or physical blowing agents are used.
  • physical blowing agents for example, carbon dioxide and / or volatile organic substances are used as blowing agents.
  • auxiliaries and additives are described for example in the EP-A 0 000 389 , Pages 18 - 21 described. Further examples of auxiliaries and additives which may optionally be used according to the invention and details of the mode of use and mode of action of these auxiliaries and additives are disclosed in US Pat Kunststoff-Handbuch, Volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff, 3rd edition, 1993, eg on pages 104-127 described.
  • Preferred catalysts are aliphatic tertiary amines (for example trimethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (for example 1,4-diaza (2,2,2) bicyclooctane), aliphatic amino ethers (for example dimethylaminoethyl ether and N, N, N-trimethyl-N- hydroxyethyl bisaminoethyl ether), cycloaliphatic amino ethers (e.g., N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, urea, derivatives of urea (such as aminoalkyl ureas, see for example EP-A 0 176 013 , in particular (3-dimethylaminopropylamine) urea) and tin catalysts (such as dibutyltin oxide, dibutyltin dilaurate, tin octo
  • catalysts are: (3-dimethylaminopropylamine) urea, 2- (2-dimethylaminoethoxy) ethanol, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N, N, N-trimethyl-N hydroxyethyl bisaminoethyl ether and 3-dimethylaminopropylamine.
  • compounds A5 having at least two isocyanate-reactive hydrogen atoms and a molecular weight of from 32 to 399 are used as component A5.
  • These are to be understood as meaning hydroxyl-containing and / or amino-containing and / or thiol-containing and / or carboxyl-containing compounds, preferably hydroxyl-containing and / or amino-containing compounds which serve as chain extenders or crosslinkers.
  • These compounds usually have 2 to 8, preferably 2 to 4, isocyanate-reactive hydrogen atoms.
  • ethanolamine, diethanolamine, triethanolamine, sorbitol and / or glycerol can be used as component A5. Further examples of compounds according to component A5 are described in EP-A 0 007 502 , Pages 16 - 17.
  • polyisocyanates as described in US Pat EP-A 0 007 502 , Pages 7 - 8.
  • polyisocyanates for example the 2,4- and 2,6-toluene diisocyanate, and any desired mixtures of these isomers (“TDI”) are preferred;
  • Polyphenylpolymethylenpolyisocyanate as prepared by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret polyisocyanates (“modified polyisocyanates"), in particular such modified polyisocyanates, which differs from the Derive 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate.
  • At least one compound selected from the group consisting of 2,4- and 2,6-tolylene diisocyanate, 4,4'- and 2,4'- and 2,2'-diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate (“multi-core MDI") is used as the polyisocyanate.
  • a mixture containing 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and Polyphenylpolymethylenpolyisocyanat is used as the polyisocyanate.
  • the reaction components are reacted according to the known one-step process, often using mechanical equipment, for example those which are used in the EP-A 355 000 to be discribed. Details about Processing devices, which are also according to the invention in question are in Plastics Handbook, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Kunststoff 1993, eg on pages 139 to 265 , described.
  • the flexible polyurethane foams can be produced as molded or also as block foams.
  • the invention therefore relates to a process for the preparation of flexible polyurethane foams, the flexible polyurethane foams produced by these processes, the flexible polyurethane foams or flexible polyurethane foams produced by these processes, the use of the flexible polyurethane foams for the production of molded parts and the moldings themselves.
  • the flexible polyurethane foams obtainable according to the invention find, for example the following uses: furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges and building components.
  • index indicates the percentage ratio of the actual amount of isocyanate used to the stoichiometric, ie calculated for the implementation of OH equivalents amount of isocyanate groups (NCO) amount.
  • identification number isocyanate - Quantity used : isocyanate - Quantity calculated • 100
  • the density was determined according to DIN EN ISO 3386-1-98.
  • the compression hardness was determined according to DIN EN ISO 3386-1-98 (at 40% deformation and 4th cycle).
  • the tensile strength and elongation at break were determined according to DIN EN ISO 1798.
  • the factor 102 results from the sum of the molar masses of CO 2 (molar mass 44 g / mol) and that of propylene oxide (molar mass 58 g / mol), the factor 58 results from the molar mass of propylene oxide and the factor 146 results from the molar mass of the employed Starters 1,8-octanediol (if available).
  • the composition based on the polymer portion (consisting of polyether polyol, which was composed of starter and propylene oxide during the activation steps taking place under CO 2 -free conditions, and polyether carbonate polyol, composed of starter, propylene oxide and carbon dioxide during to calculate the activation steps taking place in the presence of CO 2 and during the copolymerization), the non-polymer constituents of the reaction mixture (ie cyclic propylene carbonate and possibly present, unreacted propylene oxide) were computationally eliminated.
  • the indication of the CO 2 content in the polyethercarbonate polyol is normalized to the proportion of the polyethercarbonate polyol molecule which has been formed during the copolymerization and, if appropriate, the activation steps in the presence of CO 2 (ie the proportion of the polyethercarbonate polyol molecule selected from the starter (1 , 8-octanediol, if any) as well as resulting from the reaction of the initiator with epoxide added under CO 2 -free conditions was not considered).
  • the Schlifferlenmeyer flask was fitted with a riser (air cooler) and the sample was boiled for 75 minutes at low reflux.
  • the sample mixture was then transferred to a 500 ml round bottom flask and volatile components (essentially pyridine, acetic acid and excess acetic anhydride) were distilled off over a period of 30 minutes at 80 ° C and 10 mbar (absolute).
  • volatile components essentially pyridine, acetic acid and excess acetic anhydride
  • the distillation residue was then added three times with 100 ml of cyclohexane (alternatively, toluene was used in cases where the distillation residue in cyclohexane did not dissolve) and volatile components in each case at 80 ° C and 400 mbar (absolute) removed.
  • volatiles of the sample were removed for one hour at 100 ° C and 10 mbar (absolute).
  • F is the area of resonance at 2.04 ppm and 2.07 ppm, respectively.
  • polyurethane soft block foams according to the invention in which polyether carbonate polyols having a terminal block of propylene oxide (PO) and ethylene oxide (EO) were processed in a molar ratio PO / EO of 15/85 to 60/40 surprisingly had a higher Compression hardness and higher tensile strength compared to soft block foams based on a polyether polyol (A2-1, see Table 1, Comparative Example 1) or a polyether carbonate polyol having a terminal propylene oxide block (A1-2, see Table 1, Comparative Example 2).
  • PO propylene oxide
  • EO ethylene oxide

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Claims (15)

  1. Procédé de fabrication de polyéthercarbonate-polyols, caractérisé en ce que
    (i) lors d'une première étape, un polyéthercarbonate-polyol est fabriqué à partir d'une ou de plusieurs substances de départ à fonction H, à partir d'un ou de plusieurs oxydes d'alkylène et de dioxyde de carbone, en présence d'au moins un catalyseur DMC, et
    (ii) lors d'une seconde étape, le polyéthercarbonate-polyol est soumis à un allongement de chaînes avec un mélange d'au moins deux oxydes d'alkylène différents en présence d'au moins un catalyseur DMC,
    caractérisé en ce que, lors de la seconde étape (ii), un mélange contenant de l'oxyde de propylène (PO) et de l'oxyde d'éthylène (EO) en un rapport molaire PO/EO de 15/85 à 60/40 est utilisé en tant que mélange d'au moins deux oxydes d'alkylène différents.
  2. Procédé selon la revendication 1, caractérisé en ce que, lors de la première étape (i),
    (α) la substance de départ à fonction H ou un mélange d'au moins deux substances de départ à fonction H est chargé, et de l'eau et/ou d'autres composés volatils sont éventuellement éliminés par une température élevée et/ou une pression réduite (« séchage »), le catalyseur DMC étant ajouté à la substance de départ à fonction H ou au mélange d'au moins deux substances de départ à fonction H avant ou après le séchage,
    (β) pour l'activation, une partie (par rapport à la totalité de la quantité d'oxydes d'alkylène utilisée lors de l'activation et de la copolymérisation) d'un ou de plusieurs oxydes d'alkylène est ajoutée au mélange résultant de l'étape (α), cet ajout d'une partie d'oxyde d'alkylène pouvant éventuellement avoir lieu en présence de CO2, et la pointe de température (« point chaud ») qui se produit en raison de la réaction chimique exotherme suivante et/ou une chute de pression dans le réacteur étant à chaque fois attendues, et l'étape (β) pour l'activation pouvant également avoir lieu à plusieurs reprises,
    (γ) un ou plusieurs oxydes d'alkylène et du dioxyde de carbone sont ajoutés au mélange résultant de l'étape (β), les oxydes d'alkylène utilisés à l'étape (γ) pouvant être identiques ou différents des oxydes d'alkylène utilisés à l'étape (β).
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que, lors de la seconde étape (ii), un mélange constitué par de l'oxyde de propylène (PO) et de l'oxyde d'éthylène (EO) en un rapport molaire PO/EO de 15/85 à 60/40 est utilisé en tant que mélange d'au moins deux oxydes d'alkylène différents.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que, lors de la seconde étape (ii), le rapport molaire entre l'oxyde de propylène (PO) et l'oxyde d'éthylène (EO) est de 15/85 à 40/60.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que
    (iii) le polyéthercarbonate-polyol résultant de l'étape (ii) comprenant une séquence mixte terminale est soumis à un allongement de chaînes avec un oxyde d'alkylène.
  6. Polyéthercarbonate-polyol, qui contient une séquence mixte terminale constituée d'au moins deux oxydes d'alkylène, caractérisé en ce que la séquence mixte terminale contient un mélange d'oxyde de propylène (PO) et d'oxyde d'éthylène (EO) en un rapport molaire PO/EO de 15/85 à 60/40.
  7. Polyéthercarbonate-polyol selon la revendication 6, caractérisé en ce que la séquence mixte terminale est constituée d'un mélange d'oxyde de propylène (PO) et d'oxyde d'éthylène (EO) en un rapport molaire PO/EO de 15/85 à 60/40.
  8. Polyéthercarbonate-polyol selon la revendication 6 ou 7, caractérisé en ce que le rapport molaire entre l'oxyde de propylène (PO) et l'oxyde d'éthylène (EO) dans la séquence mixte est de 15/85 à 40/60.
  9. Polyéthercarbonate-polyol selon l'une quelconque des revendications 6 à 8, caractérisé en ce que la séquence mixte terminale est soumise à un allongement de chaînes avec un oxyde d'alkylène.
  10. Polyéthercarbonate-polyol selon l'une quelconque des revendications 6 à 9, caractérisé en ce que la longueur moyenne de la séquence mixte terminale constituée d'au moins deux oxydes d'alkylène différents est de 2,0 à 20,0 unités oxyde d'alkylène.
  11. Procédé de fabrication de mousses souples de polyuréthane, selon lequel un composant polyol (composant A) est utilisé, qui contient un polyéthercarbonate-polyol selon l'une quelconque des revendications 6 à 10.
  12. Procédé de fabrication de mousses souples de polyuréthane ayant une densité brute selon DIN EN ISO 3386-1-98 dans la plage allant de ≥ 10 kg/m3 à ≤ 150 kg/m3 et une dureté sous compression selon DIN EN ISO 3386-1-98 dans la plage allant de ≥ 0,5 kPa à ≤ 20 kPa (à 40 % de déformation et 4 cycles), par mise en réaction de
    un composant A contenant
    A1 100 à 10 parties en poids (par rapport à la somme des parties en poids des composants A1 et A2) de polyéthercarbonate-polyol selon l'une quelconque des revendications 6 à 10,
    A2 0 à 90 parties en poids (par rapport à la somme des parties en poids des composants A1 et A2) de polyéther-polyol classique,
    A3 0,5 à 25 parties en poids (par rapport à la somme des parties en poids des composants A1 et A2) d'eau et/ou d'un agent gonflant physique,
    A4 0,05 à 10 parties en poids (par rapport à la somme des parties en poids des composants A1 et A2) d'adjuvants et d'additifs, tels que
    d) des catalyseurs,
    e) des additifs tensioactifs,
    f) des pigments ou des agents ignifuges,
    A5 0 à 10 parties en poids (par rapport à la somme des parties en poids des composants A1 et A2) de composés comprenant des atomes d'hydrogène réactifs avec les isocyanates ayant un poids moléculaire de 62 à 399,
    avec un composant B contenant des polyisocyanates,
    la fabrication ayant lieu à un indice caractéristique de 50 à 250, et toutes les indications de parties en poids des composants A1 à A5 dans la présente demande étant normées de sorte que la somme des parties en poids des composants A1+A2 dans la composition soit de 100.
  13. Procédé selon la revendication 12, selon lequel un composant A constitué par
    A1 100 parties en poids d'un polyéthercarbonate-polyol selon l'une quelconque des revendications 6 à 10,
    A2 le composant A est exempt de polyéther-polyol classique,
    A3 0,5 à 25 parties en poids (par rapport aux parties en poids du composant A1) d'eau et/ou d'un agent gonflant physique,
    A4 0,05 à 10 parties en poids (par rapport aux parties en poids du composant A1) d'adjuvants et d'additifs, tels que
    g) des catalyseurs,
    h) des additifs tensioactifs,
    i) des pigments ou des agents ignifuges, et
    A5 0 à 10 parties en poids (par rapport aux parties en poids du composant A1) de composés comprenant des atomes d'hydrogène réactifs avec les isocyanates ayant un poids moléculaire de 62 à 399,
    est utilisé.
  14. Procédé de fabrication de mousses souples de polyuréthane, selon lequel un composant polyol (composant A) est utilisé, qui contient un polyéthercarbonate-polyol pouvant être obtenu selon l'une quelconque des revendications 1 à 5.
  15. Mousses souples de polyuréthane ayant une densité brute selon DIN EN ISO 3386-1-98 dans la plage allant de ≥ 10 kg/m3 à ≤ 150 kg/m3 et une dureté sous compression selon DIN EN ISO 3386-1-98 dans la plage allant de ≥ 0,5 kPa à ≤ 20 kPa (à 40 % de déformation et 4 cycles), pouvant être obtenues par un procédé selon l'une quelconque des revendications 11 à 14.
EP12729042.7A 2011-06-01 2012-05-30 Procédé destiné à la fabrication de polyols de polyéther Not-in-force EP2714770B1 (fr)

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WO2012130760A1 (fr) * 2011-03-28 2012-10-04 Bayer Materialscience Ag Procédé de production de mousses souples de polyuréthane
EP2730602A1 (fr) * 2012-11-09 2014-05-14 Bayer MaterialScience AG Procédé destiné à la fabrication de polyéthercarbonatpolyoles
KR20150084820A (ko) 2012-11-09 2015-07-22 바이엘 머티리얼사이언스 아게 폴리에테르 카르보네이트 폴리올의 제조 방법
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KR20140035455A (ko) 2014-03-21
BR112013030898A2 (pt) 2016-12-06
SG195061A1 (en) 2013-12-30
US20140107245A1 (en) 2014-04-17
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US20190002634A1 (en) 2019-01-03
US11130842B2 (en) 2021-09-28
CN103703052A (zh) 2014-04-02
EP2714770A1 (fr) 2014-04-09
ES2606000T3 (es) 2017-03-17
CA2837624A1 (fr) 2012-12-06

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